N-(1,3-Dioxo-2,3-dihydro-1H-isoindol-2-yl)-4,4′′-difluoro-5′-hy­droxy-1,1′:3′,1′′-terphenyl-4′-carboxamide

Hoong-Kun Fun; Tze Shyang Chia; S Samshuddin; B Narayana; B K Sarojini

doi:10.1107/S160053681203365X

. 2012 Aug 1;68(Pt 9):o2619–o2620. doi: 10.1107/S160053681203365X

N-(1,3-Dioxo-2,3-dihydro-1H-isoindol-2-yl)-4,4′′-difluoro-5′-hydroxy-1,1′:3′,1′′-terphenyl-4′-carboxamide

Hoong-Kun Fun ^a,^*,^‡, Tze Shyang Chia ^a, S Samshuddin ^b, B Narayana ^b, B K Sarojini ^c

PMCID: PMC3435648 PMID: 22969521

Abstract

The asymmetric unit of the title compound, C₂₇H₁₆F₂N₂O₄, consists of two crystallographically independent molecules (A and B). In molecule B, the isoindoline-1,3-dione ring system is disordered over two set of sites with a site-occupancy ratio of 0.658 (12):0.342 (12). In molecule A, the fluoro-substituted benzene rings make dihedral angles of 18.36 (8) and 46.37 (8)° with the central benzene ring, whereas the corresponding angles are 40.90 (8) and 52.89 (9)° in molecule B. The isoindoline ring system in molecule A and the major and minor components of the disordered isoindoline ring system in molecule B make dihedral angles of 58.50 (4), 54.13 (16) and 70.01 (28) °, respectively, with their attached benzene rings, linked through the amide group. An intramolecular O—H⋯O hydrogen bond generates an S(6) ring in each molecule. In the crystal, molecules are linked by N—H⋯O, C—H⋯F and C—H⋯O hydrogen bonds into sheets lying parallel to the bc plane. The crystal studied was a non-merohedral twin with a refined twin component ratio of 0.9316 (8):0.0684 (8).

Related literature

For related structures and background to terphenyls and their oxadiazole derivatives, see: Fun et al. (2012a ▶,b ▶); Samshuddin et al. (2011) ▶. For the planarity of isoindoline, see: Asad et al. (2011 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For the stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C₂₇H₁₆F₂N₂O₄
M _r = 470.42
Monoclinic,
a = 24.8732 (10) Å
b = 8.9875 (4) Å
c = 21.3722 (9) Å
β = 114.921 (1)°
V = 4332.9 (3) Å³
Z = 8
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 100 K
0.41 × 0.31 × 0.14 mm

Data collection

Bruker APEX DUO CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.956, T _max = 0.985
16713 measured reflections
16713 independent reflections
12698 reflections with I > 2σ(I)

Refinement

R[F ² > 2σ(F ²)] = 0.056
wR(F ²) = 0.168
S = 1.05
16713 reflections
748 parameters
45 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.63 e Å⁻³
Δρ_min = −0.90 e Å⁻³

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S160053681203365X/hb6906sup1.cif

e-68-o2619-sup1.cif^{(57.9KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681203365X/hb6906Isup2.hkl

e-68-o2619-Isup2.hkl^{(816.8KB, hkl)}

Supplementary material file. DOI: 10.1107/S160053681203365X/hb6906Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1A—H1NA⋯O2A ⁱ	0.80 (3)	2.02 (3)	2.8000 (19)	166 (3)
O1B—H1OB⋯O2B	0.88 (3)	1.79 (4)	2.5663 (17)	145 (4)
N1B—H1NB⋯O2B ⁱⁱ	0.91 (3)	2.04 (3)	2.779 (2)	138 (2)
O1A—H1OA⋯O2A	0.82 (3)	1.94 (3)	2.6402 (18)	143 (3)
C2A—H2AA⋯F2A ⁱⁱⁱ	0.93	2.45	3.160 (2)	133
C4B—H4BA⋯O3B ^iv	0.93	2.41	3.271 (7)	154
C14B—H14B⋯O3B ^v	0.93	2.44	3.293 (6)	152
C25B—H25B⋯O1B ^vi	0.93	2.47	3.209 (3)	136

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) ; (v) ; (vi) .

Acknowledgments

HKF and TSC thank Universiti Sains Malaysia (USM) for the Research University Grant (1001/PFIZIK/811160). TSC also thanks the Malaysian Government and USM for the award of a research fellowship. BN thanks the UGC for financial assistance through the SAP and BSR one-time grant for the purchase of chemicals. SS thanks Mangalore University for the research facilities.

supplementary crystallographic information

Comment

In continuation of our work on synthesis of various terphenyl derivatives (Fun et al., 2012a,b), the title compound was prepared and its crystal structure is reported. The starting material of the title compound was prepared from 4,4'-difluoro chalcone by several steps (Samshuddin et al., 2011).

The asymmetric unit of the title compound consists of two crystallographically independent molecules (A and B) as shown in Fig. 1. Each molecule contains one benzene ring [C7–C12], two fluoro-substituted benzene rings [C1–C6 & C13–C18] and an isoindoline-1,3-dione ring system [N2/O3/O4/C20–C27]. In molecule B, isoindoline-1,3-dione ring system is disordered over two positions with a site-occupancy ratio of 0.658 (12):0.342 (12). In molecule A, the fluoro-substituted benzene rings make dihedral angles of 18.36 (8) and 46.37 (8)° with the C7–C12 benzene ring, whereas the corresponding angles are 40.90 (8) and 52.89 (9)° in molecule B. The isoindoline ring systems [N2A/C20A–C27A, N2B/C20B–C27B & N2X/C20X–C27X; maximum deviations = 0.035 (1), 0.075 (4) and 0.084 (18) Å, respectively] make dihedral angles of 58.50 (4), 54.13 (16) and 70.01 (28) °, respectively with their attached C7–C12 benzene ring. An intramolecular O—H···O hydrogen bond (Table 1) generates an S(6) ring motif (Fig. 1; Bernstein et al., 1995) in each molecule. The bond lengths and angles are comparable to those found in related structures (Fun et al., 2012a,b)

In the crystal (Fig. 2), molecules are linked by N1A—H1NA···O2A, N1B—H1NB···O2B, C2A—H2AA···F2A, C4B—H4BA···O3B, C14B—H14B···O3B and C25B—H25B···O1B hydrogen bonds into sheets parallel to bc plane.

Experimental

A mixture of 4,4''-difluoro-5'-hydroxy-1,1':3',1''-terphenyl-4'-carbohydrazide (3.40 g, 0.01 mol) and phthalic anhydride (1.48 g, 0.01 mol) was dissolved in acetic acid (25 ml) and heated to reflux for 6 h. The reaction mixture was then poured into ice cold water, filtered and crystallized from ethanol. Colourless blocks were grown from DMF solution by slow evaporation method and yield of the compound was 76%. (m.p. 506 K).